US3700667A - Method for manufacturing purified isocyanurates - Google Patents

Method for manufacturing purified isocyanurates Download PDF

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Publication number
US3700667A
US3700667A US119939A US3700667DA US3700667A US 3700667 A US3700667 A US 3700667A US 119939 A US119939 A US 119939A US 3700667D A US3700667D A US 3700667DA US 3700667 A US3700667 A US 3700667A
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weight
amine
isocyanurates
isocyanurate
hydrazine
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US119939A
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Hisao Kitano
Fumio Tanimoto
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/34—Cyanuric or isocyanuric esters

Definitions

  • the present invention relates to a method for removing impurities from crude isocyanurates, more particularly relates to a method for purifying various crude isocyanurates which have been industrially produced by known processes.
  • a process according to the present invention which comprises contacting isocyanurates containing from 0.01 to 10.00% by weight om impurities with a basic solution containing at least 5% by weight of a nitrogen containing compound selected from the group consisting of ammonia, hydrazine, alkylamine, alkylhydrazine, alkenylamine, alkanol amine, alkylene amine, alkanol hydrazine and acid amide having 0 to 4 carbon atoms, at a temperature between 20 and 200 C. and under a pressure between 1.5 and 30 kg./cm.
  • a nitrogen containing compound selected from the group consisting of ammonia, hydrazine, alkylamine, alkylhydrazine, alkenylamine, alkanol amine, alkylene amine, alkanol hydrazine and acid amide having 0 to 4 carbon atoms
  • the nitrogen containing compounds selected from the group consisting of ammonia, hydrazine, alkyl amine, alkyl hydrazine, alkenyl amine, alkanol amine, alkylene amine, alkanol hydrazine and acid amide having 0 to 4 carbon atoms can be employed alone or as an admixture thereof. And common characteristics of these compounds are that they are basic, water-soluble and have a sufficient afiinity to various solvents.
  • nitrogen containing compounds include, for example, ammonia, methyl amine, dimethyl amine, trimethyl amine, aqueous ammonia, tetramethyl ammonium hydroxide-water solution, ethyl amine, diethyl amine, propyl amine, isopropyl amine, sec-butyl amine, tert.-butyl amine, isobutyl amine, hydrazine, hydrazine hydrate, methyl hydrazine, ethyl hydrazine, dimethyl hydrazine, diethyl hydrazine, propyl hydrazine, isopropyl hydrazine, butyl hydrazine, sec.-butyl hydrazine, tert.-butyl hydrazine, allyl amine, crotyl amine, methallyl amine, ethanol amine, diethanol amine, propanol amine
  • especially advantageous compounds among aforesaid compounds are ammonia, aqueous ammonia, alcoholic ammonia, methyl amine, dimethyl amine, liquid ammonia, ethyl amine, diethyl amine, hydrazine, ethanol amine, ethylene diamine, dimethyl formamide, and urea, etc.
  • the nitrogen containing compound above described is used as basic solution containing at least 5% by Weight of at least one of compound selected from aforesaid nitrogen containing compounds, which is prepared by adding from 5 to by Weight of at least one aforesaid nitrogen containing compound to neutral or basic solvent such as water, liquid ammonia, hydrazine hydrate, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, ethanol amine, ethylene diamine, tert.-amine, for example, pyridine.
  • 100% solution of nitrogen containing compound refers to liquid comprising liquid ammonia, hydrazine hydrate, ethanol amine or ethylene diamine which are liquid in normal condition.
  • a concentration of said nitrogen containing compound in the basic solution is variable depending on the reaction conditions.
  • the basic solution containing at least 5% by Weight, preferably more than 15% by Weight of a nitrogen containing compound selected from said group in view of aforesaid studies and logical treating time of crude isocyanurates.
  • Isocyanurates can be synthesized by reacting halogenohydrocarbons with alkali cyanates or alkali cyanurates, or by a rearrangement reaction of cyanurates and the like and the resulted crude isocyanurates usually contain from 0.01 to 10.00% by Weight of impurities.
  • Said impurities include various kinds of chemical material, and usually being cyanuric acid and cyanurates, parabanic acid and parabanates, 1,3-disubstituted urea, organic carbonates, monoor di-esters of isocyanuric acid, quaternary ammonium salts, alkyl halides, alkali halides, cyamelide, tarry materials or mixtures of these chemical material.
  • the content of the impurities in said crude isocyanurates should be between 0.01 and 10.00% by weight, most preferably between 0.05 and 8.00% by weight.
  • the purification process of the present invention can not be carried out advantageously. So that the other process, described before, should be applied to such crude isocyanurates.
  • the conditions employed in the present invention were experimentally determined so as that pressure was 'between 1.5 and 30 kg./cm. temperature being between 20 and 200 C. These conditions are essential in order to remove and/or decompose the impurities in crude isocyanurates.
  • An acceptable pressure for the purpose of the present invention is between 1.5 and 30 kg./cm. most preferably between 3 and 25 kg./cm.
  • the pressure can be induced by utilizing a vapour pressure of the nitrogen containing compounds such as ammonia and the like or said solvent of the basic solution, for example, water, alcohol or ammonia, etc., or by forcedly introducing air or nitrogen gas.
  • the process of the present invention intends to remove specific amounts of impurities of crude isocyanurates. This process can be carried out in a stage of purification combined with continuous or batch system of synthesis of isocyanurates.
  • the process of the present invention can be conducted in a simple apparatus such as reactor system, pipe system and the like.
  • the treating period of the process of the present invention is normally between 0.2 and 20.0 hours, and preferably between 0.5 and 5.0 hours.
  • the system After the treatment of crude isocyanurates according to the present invention, the system must be depressurized to normal pressure and the resulted purified isocyanurates must be separated from the basic solution, because the process of the present invention is conducted under the pressure. Said separation can be carried out by any way of fractionation, extraction, distillation and crystallization or an appropriate combination of these operations.
  • the purities of the resulting purified isocyanurates according to the present invention can be determined by elementary analysis (nitrogen content) or gas chromatography.
  • the purities of the isocyanurates containing unsaturated hydrocarbons can be detected by determination of bromine number or maximum exothermic temperature of polymerization. And when the resulted purified isocyanurates have melting points, the optimal sharp points should be deemed as their purities.
  • EXAMPLE 1 500 g. of crude triallyl isocyanurate, which contains 1.2% by weight of diallyl carbonate, 0.7% by weight of dimethyl allyl amine hydrochloride and 0.2% by Weight of tarry materials, are dissolved in 1000 ml. of methanol. To the solution 300 g. of ammonia is added. And the mixture is introduced into an autoclave and allowed to stand at 100 C. under a pressure between 5 and 7 kg./cm. for 3 hours, thereafter it is cooled. When the mixture is put into water, an oily material is layered. The oily material is collected and distilled to give trially isocyanurate with a purity 'of more than 99% by weight. The yield is 460 g.
  • EXAMPLE 3 A mixture of 5 g. of hydrazine hydrate 200 ml. of pyridine and 100 g. of crude trimethyl isocyanurate containing 0.8% by weight of cyanuric acid, 0.1% by weight of dimethyl parabanate and 1.1% by weight of 1,3-dimethyl urea is introduced into an autoclave and allowed to stand at 150 C. under a pressure between 5 and 6 atmospheric pressures by nitrogen gas. After cooling the resulting mixture from the autoclave is put into a cold water to give crystal. Collecting the crystal, it is recrystalled from water-methanol to give 92 g. of trimethyl isocyanurate with a purity of more than 99% by weight.
  • EXAMPLE 5 100 g. of crude-tri-n-amyl isocyanurate containing 0.05% by weight of n-amyl chloride is put into an autoclave altogether with 100 ml. of 25% aqueous ammonia. and 50 ml. of dimethyl formamide, allowed to stand at a temperature between 80 and C. at a pressure of 4 atm. for 10 hours. The mixture is cooled, poured into water, then extracted with toluene. The extract is distilled to give g. of pure tri-n-amyl isocyanurate.
  • EXAMPLE 6 A mixture of around equivalent volume of liquid ammonia to crude triallyl isocyanurate containing 2.8% by weight of diallyl carbonate, 0.8% by weight of 1,3- diallyl urea and a trace amount of sodium chloride are passed through a steel pipe heated to 60 C. during an hour. At the time the pressure used is about 25 kg./cm. which is caused by a size of the steel pipe and a fluidity of the materials. After cooling the mixture, the ammonia is removed, the residue is put into water. It is washed with 5% hydrochloric acid, then washed with water and fractionated to obtain an oily material. The oily material is fractionally distilled to give triallyl isocyanurate with a purity of more than 99%. The yield is about 95%.
  • EXAMPLE 7 100 g. of crude diallyl propyl isocyanurate containing 5.5% by weight of diallyl isocyanurate are put in 200 g. of ethanol amine containing 3% by weight of methyl amine and 3% by weight of dimethyl amine and the mixture is introduced into a pressure reactor, it is vigorously stirred at 150 C. under a nitrogen pressure of 28 atm. for 7 hours. After cooling the mixture it is extracted with benzene, the resulting extract is washed with water, then distilled to give 90 g. of diallyl propyl isocyanurate 'with a purity of more than 98% EXAMPLE 8 200 g.
  • EXAMPLE 9 150 g. of cmde triallyl isocyanurate containing 3.7% by weight of diallyl carbonate, 50 g. of ammonia, 10 g. of urea, and 100 g. of Water are put in a pressure reactor, the mixture is vigorously stirred at a temperature between 60 and 70 C. at a pressure of 13 atm. for 2 hours, it is cooled, then the resulted precipitate is recovered and it is deeply cooled to give crystal. After filtrating the crystal it is washed with water, dried at a lower temperature under a reduced pressure to give 140 g. of triallyl isocyanurate with a purity of more than 98.5%.
  • EXAMPLE 10 150 g. of crude trialauryl isocyanurate containing 1.8% by weight of 1,3-dilauryl, and 50 g. of liquid ammonia are contacted in a pressure reactor at 35 C. for 3 hours, then the mixture is cooled by introducing 200 ml. of methanol to the pressure reactor. The resulting mixture is withdrawn and the ether layer is removed, the residue is redissolved in ligroin thereby recrystallizing to give 136 g. of pure trilauryl isocyanurate.
  • EXAMPLE 11 100 g. of crude tri-n-propyl isocyanurate containing 5% by weight of di-n-propyl carbonate are dissolved in 200 g. of ethanol containing by weight of a reagent shown in Table I, the mixture is put in an autoclave, it is allowed to stand at 97 C. for 3 hours.
  • tripropargyl isocyanurate containing 2.0% by weight of 1,3-dipropargyl urea, and 20 g. of 3040% ammoniac methanol are charged in a sealed tube, the mixture is allowed to stand at a temperature between 60 and C. at a pressure between 1.5 and 2.0 atm. for an hour. The resulting mixture is sufliciently cooled to precipitate crystal, then the crystal is collected and it is allowed to recrystal from methanol to give 8 g. of tripropargyl isocyanurate with a purity of more than 99%.
  • a method of manufacturing purified isocyanurate which comprises treating crude trialkyl isocyanurate containing from 0.01% to 10.00% by weight of impurities with basic solution containing at least 5% by weight of a nitrogen compound selected from the group consisting of ammonia, hydrazine, alkyl amine, alkyl hydrazine, alkenyll amine, alkanol amine, alkylene amine, alkanol hydrazine and :acid amide having from 0 to 4 of carbon atoms, at a temperature between 20 C. and 200 C. and under a pressure between 1.5 kg./cm. and 30 kg./cm.
  • a nitrogen compound selected from the group consisting of ammonia, hydrazine, alkyl amine, alkyl hydrazine, alkenyll amine, alkanol amine, alkylene amine, alkanol hydrazine and :acid amide having from 0 to 4 of carbon atoms,
  • trialkyl isocyanurate is one selected from the group consisting of trimethyl isocyanurate, tripropyl isocyanurate, n'ibutyl isocyanurate, triamyl isocyanurate and trilauryl isocyanurate.
  • a method of manufacturing purified isocyanurate which comprises treating crude isocyanurate having unsaturated hydrocarbon radical containing from 0.01% to 10.00% by weight of impurities with basic solution containing at least 5% by weight of a nitrogen compound selected from the group consisting of ammonia, hydrazine, alkyl amine, alkyl hydrazine, alkenyl amine, alkanol amine, alkylene amine, alkanol hydrazine and acid amide having from 0 to 4 of carbon atoms, at a temperature between 20 C. and 200 C., under a pressure between 1.5 kgJcm. and 30 kg./cm.
  • a method of manufacturing purified triallyl isocyanurate which comprises treating crude triallyl isocyanurate containing from 0.01% to 10.00% by weight of impurities with basic solution containing at least 5% by weight of a nitrogen compound selected from the group consisting of ammonia, ammonia added sodium amide and urea, at a temperature between20 C. and 100 C., under a pressure between .1.5 kg./cm. and 30 kgjcmfl.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US119939A 1970-03-02 1971-03-01 Method for manufacturing purified isocyanurates Expired - Lifetime US3700667A (en)

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JP1809570A JPS4722588B1 (enrdf_load_stackoverflow) 1970-03-02 1970-03-02

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JP (1) JPS4722588B1 (enrdf_load_stackoverflow)
GB (1) GB1305513A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016164A (en) * 1974-03-04 1977-04-05 Fmc Corporation Process for purifying crude cyanuric acid
US5227416A (en) * 1991-12-23 1993-07-13 Ppg Industries, Inc. Intumescent flame retardant composition
JP2011006389A (ja) * 2009-05-25 2011-01-13 Nippon Kasei Chem Co Ltd トリアリルイソシアヌレート、トリアリルシアヌレート及びトリアリルイソシアヌレートの製造方法
CN102448944A (zh) * 2009-05-25 2012-05-09 日本化成株式会社 异氰脲酸三烯丙酯及其制造方法
US9587061B2 (en) 2014-12-19 2017-03-07 Evonik Degussa Gmbh Co-crosslinker systems for encapsulation films comprising urea compounds
US10233275B2 (en) 2014-12-19 2019-03-19 Evonik Degussa Gmbh Co-crosslinker systems for encapsulation films comprising BIS(alkenylamide) compounds
CN115403609A (zh) * 2022-05-09 2022-11-29 江苏瑞洋安泰新材料科技有限公司 一种异氰脲酸三[3-(三甲氧基硅烷基)丙基]酯的制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60134558U (ja) * 1984-02-16 1985-09-07 金鹿鏝工業株式会社 デイスクサンダ−
KR101774225B1 (ko) * 2009-05-25 2017-09-04 니폰 가세이 가부시키가이샤 트리알릴 이소시아누레이트의 저장방법

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016164A (en) * 1974-03-04 1977-04-05 Fmc Corporation Process for purifying crude cyanuric acid
US5227416A (en) * 1991-12-23 1993-07-13 Ppg Industries, Inc. Intumescent flame retardant composition
US8674092B2 (en) 2009-05-25 2014-03-18 Nippon Kasei Chemical Company Limited Triallyl isocyanurate and process for producing the same
EP2436677A1 (en) 2009-05-25 2012-04-04 Nippon Kasei Chemical Company Limited Triallylisocyanurate, triallylcyanurate, and process for production of triallylisocyanurate
CN102448944A (zh) * 2009-05-25 2012-05-09 日本化成株式会社 异氰脲酸三烯丙酯及其制造方法
EP2436678A4 (en) * 2009-05-25 2012-11-07 Nippon Kasei Chem TRIALLYLISOCYANURATE AND MANUFACTURING METHOD THEREFOR
JP2011006389A (ja) * 2009-05-25 2011-01-13 Nippon Kasei Chem Co Ltd トリアリルイソシアヌレート、トリアリルシアヌレート及びトリアリルイソシアヌレートの製造方法
EP2899184A1 (en) * 2009-05-25 2015-07-29 Nippon Kasei Chemical Co., Ltd. Use of triallyl isocyanurate
CN102448944B (zh) * 2009-05-25 2017-06-20 日本化成株式会社 异氰脲酸三烯丙酯及其制造方法
US9587061B2 (en) 2014-12-19 2017-03-07 Evonik Degussa Gmbh Co-crosslinker systems for encapsulation films comprising urea compounds
US10233275B2 (en) 2014-12-19 2019-03-19 Evonik Degussa Gmbh Co-crosslinker systems for encapsulation films comprising BIS(alkenylamide) compounds
CN115403609A (zh) * 2022-05-09 2022-11-29 江苏瑞洋安泰新材料科技有限公司 一种异氰脲酸三[3-(三甲氧基硅烷基)丙基]酯的制备方法
CN115403609B (zh) * 2022-05-09 2023-11-03 江苏瑞洋安泰新材料科技有限公司 一种异氰脲酸三[3-(三甲氧基硅烷基)丙基]酯的制备方法

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GB1305513A (enrdf_load_stackoverflow) 1973-02-07

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